Method for treating keratin fibers using a composition comprising at least one cationic acrylic copolymer and at least one pigment

ABSTRACT

A method for treating human keratin fibers such as the hair is described and comprises the application to the keratin fibers of a dye composition comprising at least one cationic acrylic copolymer and at least one pigment, and the application to the dyed keratin fibers of a makeup-removing composition comprising at least one hydrocarbon oil.

CROSS REFERENCE TO RELATED APPLICATION

This is a national stage application of PCT/EP2019/078446, filed internationally on Oct. 18, 2019, which claims priority to French Application No. 1859874, filed on Oct. 25, 2018, both of which are incorporated by reference herein in their entireties.

The subject of the present invention is a method for treating keratin fibers such as the hair, comprising the application to the keratin fibers of a dye composition comprising at least one cationic acrylic copolymer and at least one pigment, and the application to the dyed keratin fibers of a makeup-removing composition comprising at least one hydrocarbon oil.

In the field of dyeing keratin fibers, in particular human keratin fibers, it is already known practice to dye keratin fibers via various techniques using direct dyes or pigments for non-permanent dyeing, or dye precursors for permanent dyeing.

There are essentially three types of process for dyeing the hair:

a) “permanent” dyeing, the function of which is to afford a substantial modification to the natural color and which uses oxidation dyes which penetrate into the hair fiber and forms the dye via an oxidative condensation process;

b) non-permanent, semi-permanent or direct dyeing, which does not use the oxidative condensation process and withstands four or five shampoo washes; it consists in dyeing keratin fibers with dye compositions containing direct dyes. These dyes are colored and coloring molecules that have affinity for keratin fibers;

c) temporary dyeing, which gives rise to a modification of the natural color of the head of hair that remains from one shampoo wash to the next, and which serves to enhance or correct a shade that has already been obtained. It may also be likened to a “makeup” process.

For this last type of dyeing, it is known practice to use colored polymers formed by grafting one or more dyes of azo, triphenylmethane, azine, indoamine or anthraquinone nature onto a polymer chain. These colored polymers are not entirely satisfactory, especially as regards the homogeneity of the coloring obtained and its resistance, not to mention the problems associated with their manufacture and especially with their reproducibility.

Another dyeing method consists in using pigments. Specifically, the use of pigment on the surface of keratin fibers generally makes it possible to obtain visible colorings on dark hair, since the surface pigment masks the natural color of the fiber. The use of pigment for dyeing keratin fibers is described, for example, in patent application FR 2 741 530, which recommends using, for the temporary dyeing of keratin fibers, a composition comprising at least one dispersion of film-forming polymer particles comprising at least one acid function and at least one pigment dispersed in the continuous phase of said dispersion. The colorings obtained via this dyeing method have the drawback of having a low resistance to shampoo washes.

It is moreover known practice to color coat the hair using a composition comprising an electrophilic monomer of cyanoacrylate type, and a pigment, in particular in document EP 1 649 898. Such a composition makes it possible to obtain completely coated and non-greasy hair. However, the coating obtained is not entirely satisfactory in the face of external agents such as washing and perspiration. Moreover, the coating obtained is sensitive to fatty substances such as sebum.

In addition, compositions for temporarily dyeing the hair may also lead to a hair feel that is uncosmetic and/or not natural; the hair thus dyed may in particular lack softness and/or suppleness and/or strand separation.

Moreover, these temporary hair dye compositions may also have the drawback of transferring, i.e. of becoming at least partly deposited, leaving marks, on certain supports with which they may be placed in contact and in particular clothing or the skin.

In addition, there are no effective makeup-removing compositions for removing this type of temporary dye composition when it is resistant to shampoo washes.

Therefore there remains a need for a method for treating keratin fibers, in particular hair, which has the advantage of obtaining a homogeneous and smooth colored coating on the hair, and also hair with complete strand separation, while forming a coating that is resistant to shampoo washes and to the various attacking factors to which hair may be subjected without degradation of the keratin fibers and which is easily removed.

Thus, the objective of the present invention is to develop a method for treating keratin fibers which has the advantage of obtaining a homogeneous and smooth colored coating on the hair, and also hair with complete strand separation, while forming a coating that is resistant to shampoo washes and to the various attacking factors to which hair may be subjected without degradation of the keratin fibers and which is easily removed.

This objective is achieved with the present invention, the subject of which is a method for treating human keratin fibers such as the hair, comprising the following steps:

-   -   a) applying to the keratin fibers a dye composition comprising:         -   at least one cationic acrylic copolymer comprising at least             the units obtained from the following monomers:             -   a) monomer derived from acrylic or methacrylic esters or                 amides and comprising at least one cationic group, and             -   b) alkyl acrylate or methacrylate monomer, and         -   at least one pigment, and     -   b) applying to the dyed keratin fibers a makeup-removing         composition comprising at least one hydrocarbon oil.

Through the use of this method, colored coatings are obtained on the keratin fibers that make it possible to obtain a coloring that is visible on all types of hair in a shampoo-resistant manner while preserving the physical qualities of the keratin fibers. Such a coating may be resistant to the external attacking factors to which the hair may be subjected, such as blow-drying and perspiration. This method makes it possible to obtain hair with complete strand separation, that can be styled without problems, and from which the makeup can be removed easily either immediately after the application of the dye composition or after a certain time, i.e. a few days to a few weeks, after the application of the dye composition.

The term “hair with strand separation” means hair which, after application of the composition and drying, is not stuck together (or of which all the strands are separated from each other) and thus does not form clumps of hair.

For the purposes of the present invention, the term “shampoo-resistant coloring” means that the coloring obtained remains after one shampoo wash, preferably after 3 shampoo washes, more preferentially after 5 shampoo washes, more preferentially still after 10 shampoo washes.

The invention is not limited to the examples illustrated. The features of the various examples may notably be combined within variants which are not illustrated.

The expression “comprising a” should be understood as meaning “comprising at least one”, unless specified to the contrary.

The expression “at least one” means “one or more”.

The treatment method is preferably a cosmetic treatment method comprising a step of dyeing keratin fibers such as the hair followed by a step of removing makeup from and/or cleansing keratin fibers such as the hair.

The method according to the invention comprises a step of applying a dye composition to keratin fibers such as the hair.

Dye Composition

The dye composition according to the invention is preferably a cosmetic composition for dyeing keratin fibers, in particular human keratin fibers such as the hair.

Cationic Acrylic Copolymer

The dye composition according to the method according to the invention comprises at least one cationic acrylic copolymer, comprising at least the units obtained from the following monomers:

-   -   a) monomer derived from acrylic or methacrylic esters or amides         and comprising at least one cationic group, and     -   b) alkyl acrylate or methacrylate monomer, the alkyl radical         preferably comprising from 1 to 30 carbon atoms, preferentially         from 1 to 22 carbon atoms, better still 1 to 10 carbon atoms,         and more preferentially 2 to 6 carbon atoms.

A cationic group or compound is understood for the purposes of the present invention to mean a group or compound bearing a permanent cationic charge or else a charge obtained by protonation of a (cationizable) function, such as an amine function, by the protons of the medium.

Preferably, the copolymer according to the invention is water insoluble. For the purposes of the present invention, the term “water insoluble” means a compound that is insoluble in water at ordinary temperature (25° C.) and at atmospheric pressure (760 mmHg or 1.013×10⁵ Pa) (solubility of less than 5% and preferably less than 1%, more preferentially still less than 0.1%).

Preferentially, the cationic acrylic copolymer contains c) at least one third unit obtained from a polymerizable ethylenic monomer, preferably from a monomer of the following formula:

wherein R and R′, which may be identical or different, represent a hydrogen atom, a C₁-C₁₀, preferably C₁-C₄, alkyl radical; preferably R is a methyl radical; better still R is a methyl radical and R′ is an ethyl radical;

x ranging from 1 to 10, preferably from 1 to 3, better still x is equal to 1.

More particularly, the cationic acrylic copolymer comprises at least units obtained from the two lists of following monomers:

-   -   a) monomer derived from acrylic or methacrylic esters or amides         and comprising at least one cationic group of the following         formulae

wherein:

-   -   -   R₃, which may be identical or different, denote a hydrogen             atom or a CH₃ group;         -   A, which may be identical or different, represent a linear             or branched divalent alkyl group, with 1 to 6 carbon atoms,             preferably 2 or 3 carbon atoms, or a hydroxyalkyl group with             1 to 4 carbon atoms;         -   R₄, R₅, R₆, which may be identical or different, represent             an alkyl group having from 1 to 18 carbon atoms or a benzyl             group; preferably an alkyl group having from 1 to 6 carbon             atoms;         -   R₁ and R₂, which may be identical or different, represent a             hydrogen atom or an alkyl group having from 1 to 6 carbon             atoms, preferably methyl or ethyl;         -   X⁻ denotes an anion derived from a mineral or organic acid             such as a methosulfate anion or a halide such as chloride or             bromide.

    -   b) C₁-C₃₀, preferably C₁-C₂₂, preferentially C₁-C₁₀ and better         still C₂-C₆ alkyl acrylate or methacrylate monomer.         Even more preferentially, the cationic acrylic copolymer         comprises at least the units obtained from the following         monomers:

    -   a) monomer derived from acrylic or methacrylic esters or amides         and comprising at least one cationic group of the following         formulae:

wherein:

-   -   -   R₃, which may be identical or different, denote a hydrogen             atom or a CH₃ group;         -   A, which may be identical or different, represent a linear             or branched divalent alkyl group, with 1 to 6 carbon atoms,             preferably 2 or 3 carbon atoms, or a hydroxyalkyl group with             1 to 4 carbon atoms;         -   R₄, R₅, R₆, which may be identical or different, represent             an alkyl group having from 1 to 18 carbon atoms or a benzyl             group; preferably an alkyl group having from 1 to 6 carbon             atoms;         -   R₁ and R₂, which may be identical or different, represent a             hydrogen atom or an alkyl group having from 1 to 6 carbon             atoms, preferably methyl or ethyl;         -   X⁻ denotes an anion derived from a mineral or organic acid             such as a methosulfate anion or a halide such as chloride or             bromide,             preferably, formulae (I) and (II)

    -   b) C₁-C₃₀, preferably C₁-C₂₂, preferentially C₁-C₁₀ and better         still C₂-C₆ alkyl acrylate or methacrylate monomer         and

    -   c) polymerizable ethylenic monomer, preferably from a monomer of         the following formula

wherein R and R′, which may be identical or different, represent a hydrogen atom, a C₁-C₁₀, preferably C₁-C₄, alkyl radical; preferably R is a methyl radical; better still R is a methyl radical and R′ is an ethyl radical;

x ranging from 1 to 10, preferably from 1 to 3, better still x is equal to 1.

Even more particularly, the dye composition of use in the method according to the invention comprises at least one cationic acrylic copolymer comprising at least the units obtained from the following monomers:

-   -   a) a monomer derived from acrylic or methacrylic esters of         formula (I), or (II) as described above, preferably of formula         (II),     -   b) a C₁-C₂₂, preferably C₁-C₁₀ and better still C₂-C₆ alkyl         acrylate or methacrylate monomer.     -   c) a monomer of formula (A′) as described above.         Most particularly, the dye composition comprises at least one         cationic acrylic copolymer, preferably insoluble in water with         the following units:     -   a) methacryloyloxyethyltrimethylammonium salt,     -   b) butyl methacrylate and     -   c) ethoxyethyl methacrylate.         Such copolymers are for example described in the document         JP5745266. Preferably, the polymer contains the preceding three         monomers in the following proportions with respect to the total         of monomer units, by weight in the constituted copolymer,         without taking their salts into account:     -   a) in a proportion of 0.5% to 20%, preferably between 1% and 5%;     -   b) in a proportion of 20% to 98%, preferably between 40% and         97%, and     -   c) in a proportion of 1.5% to 95%, preferably between 2% and         55%.         Preferably, the copolymer is not amphoteric, that is to say that         it does not comprise units bearing an anionic charge.         Preferably, the units of the copolymer are all derived from         methacrylate.

More particularly still, the copolymer corresponds to the copolymer with the INCI name Polyquaternium-99, such as for example the polymer sold by GOO Chemical under the name Plascize L-514.

It is the butyl methacrylate/ethoxyethyl methacrylate/methacryloyloxyethyl trimethylammonium chloride copolymer, at 30% in ethanol:

The cationic acrylic copolymer may be present in a total amount ranging from 1% to 50% by weight, preferably from 2% to 40% by weight, more preferentially from 3% to 30% by weight and better still from 5% to 20% by weight relative to the total weight of the dye composition.

Pigments

The dye composition comprises one or more pigments.

The term “pigment” means white or colored particles of any shape, which are insoluble composition in which they are present.

The pigments that may be used are especially chosen from the organic and/or mineral pigments known in the art, notably those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.

They may be natural, of natural origin, or non-natural.

These pigments may be in pigment powder or paste form. They may be coated or uncoated.

The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof.

The pigment may be a mineral pigment. The term “mineral pigment” means any pigment that satisfies the definition in Ullmann's encyclopedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of ochres such as red ochre (clay (in particular kaolinite) and iron hydroxide (for example hematite)), brown ochre (clay (in particular kaolinite) and limonite), yellow ochre (clay (in particular kaolinite) and goethite); titanium dioxide, optionally surface treated; zirconium oxide or cerium oxide; zinc oxide, iron oxide (black, yellow or red) or chromium oxide; manganese violet, ultramarine blue, chromium hydrate and ferric blue; metal powders such as aluminum powder or copper powder.

Mention may also be made of alkaline-earth metal carbonates (such as calcium carbonate or magnesium carbonate), silicon dioxide, quartz and any other compound used as inert filler in cosmetic compositions, provided that these compounds contribute color or whiteness to the composition under the conditions under which they are employed.

The pigment may be an organic pigment. The term “organic pigment” means any pigment that satisfies the definition in Ullmann's encyclopedia in the chapter on organic pigments.

The organic pigment may especially be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

Use may also be made of any mineral or organic compound that is insoluble in the composition and standard in the cosmetics field, provided that these compounds contribute color or whiteness to the composition under the conditions under which they are employed, for example guanine, which, according to the refractive index of the composition, is a pigment.

In particular, the white or colored organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.

Examples that may also be mentioned include pigment pastes of organic pigment, such as the products sold by the company Hoechst under the names:

-   -   Cosmenyl Yellow IOG: Yellow 3 pigment (CI 11710);     -   Cosmenyl Yellow G: Yellow 1 pigment (CI 11680);     -   Cosmenyl Orange GR: Orange 43 pigment (CI 71105);     -   Cosmenyl Red R: Red 4 pigment (CI 12085);     -   Carmine Cosmenyl FB: Red 5 pigment (CI 12490);     -   Cosmenyl Violet RL: Violet 23 pigment (CI 51319);     -   Cosmenyl Blue A2R: Blue 15.1 pigment (CI 74160);     -   Cosmenyl Green GG: Green 7 pigment (CI 74260);     -   Cosmenyl Black R: Black 7 pigment (CI 77266).

The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may be composed notably of particles comprising a mineral core, at least one binder, for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core.

The organic pigment may also be a lake. The term “lake” means dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.

The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

Among the dyes, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 47 005), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (CI 15 850:1).

The pigment may also be a pigment with special effects. The term “pigments with special effects” means pigments that generally create a colored appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby contrast with colored pigments, which afford a conventional opaque, semitransparent or transparent, uniform color.

Several types of pigment with special effects exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.

Examples of pigments with special effects that may be mentioned include nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as mica coated with titanium and iron oxides, mica coated with iron oxide, mica coated with titanium and especially with ferric blue or with chromium oxide, mica coated with titanium and with an organic pigment as defined above, and also nacreous pigments based on bismuth oxychloride. Nacreous pigments that may be mentioned include the Cellini nacres sold by Engelhard (mica-TiO₂-lake), Prestige sold by Eckart (mica-TiO₂), Prestige Bronze sold by Eckart (mica-Fe₂O₃), and Colorona sold by Merck (mica-TiO₂—Fe₂O₃).

Mention may also be made of the gold-colored nacres sold especially by Engelhard under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold especially by Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by Engelhard under the name Super bronze (Cloisonne); the orange nacres sold especially by Engelhard under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown-colored nacres sold especially by Engelhard under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a coppery glint sold especially by Engelhard under the name Copper 340A (Timica); the nacres with a red glint sold especially by Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow glint sold especially by Engelhard under the name Yellow (4502) (Chromalite); the red-colored nacres with a gold glint sold especially by Engelhard under the name Sunstone G012 (Gemtone); the pink nacres sold especially by Engelhard under the name Tan opale G005 (Gemtone); the black nacres with a gold glint sold especially by Engelhard under the name Nu antique bronze 240 AB (Timica), the blue nacres sold especially by Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery glint sold especially by Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold especially by Merck under the name Indian summer (Xirona), and mixtures thereof.

Still as examples of nacres, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

Particles comprising a glass substrate coated with titanium oxide are sold in particular under the name Metashine MC1080RY by the company Toyal.

Finally, as examples of nacres, mention may also be made of polyethylene terephthalate glitter flakes, especially those sold by the company Meadowbrook Inventions under the name Silver 1P 0.004×0.004 (silver glitter flakes).

It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

The pigments with special effects may also be chosen from reflective particles, i.e. especially from particles whose size, structure, especially the thickness of the layer(s) of which they are made and their physical and chemical natures, and surface finish, allow them to reflect incident light. This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. more luminous points that contrast with their environment by appearing to sparkle.

The reflective particles may be selected so as not to significantly alter the coloring effect generated by the coloring agents with which they are combined, and more particularly so as to optimize this effect in terms of color rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery color or glint.

These particles may have varied forms and may especially be in platelet or globular form, in particular in spherical form.

Irrespective of their form, the reflective particles may or may not have a multilayer structure, and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, especially of a reflective material.

When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, especially titanium or iron oxides obtained synthetically.

When the reflective particles have a multilayer structure, they may comprise, for example, a natural or synthetic substrate, especially a synthetic substrate at least partially coated with at least one layer of a reflective material, especially of at least one metal or metallic material. The substrate may be made of one or more organic and/or mineral materials.

More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, especially aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.

The reflective material may comprise a layer of metal or of a metallic material.

Reflective particles are described especially in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

Again as an example of reflective particles including a mineral substrate coated with a layer of metal, mention may also be made of particles including a silver-coated borosilicate substrate.

Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal. Particles with a glass substrate coated with nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.

Use may also be made of particles comprising a metal substrate, such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

Examples that may be mentioned include aluminum powder, bronze powder or copper powder coated with SiO₂ sold under the name Visionaire by Eckart.

Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek). Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.

Quantum dots are luminescent semiconductor nanoparticles that are capable of emitting, under light excitation, radiation with a wavelength of between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they may be synthesized according to the processes described, for example, in U.S. Pat. Nos. 6,225,198 or 5,990,479, in the publications cited therein and also in the following publications: Dabboussi B. O. et al., “(CdSe)ZnS core-shell quantum dots: synthesis and characterisation of a size series of highly luminescent nanocrystallites”, Journal of Physical Chemistry B, vol. 101, 1997, pages 9463-9475, and Peng, Xiaogang et al., “Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility”, Journal of the American Chemical Society, vol. 119, No. 30, pages 7019-7029.

The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colors, and also particular optical effects such as metallic effects or interference effects.

The size of the pigment used in the dye composition according to the present invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm and more preferably between 30 nm and 50 μm.

The pigments may be dispersed in the product by means of a dispersant.

The dispersant serves to protect the dispersed particles against agglomeration or flocculation thereof. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, 12-hydroxystearic acid esters in particular and C₈ to C₂₀ fatty acid esters of polyols such as glycerol or diglycerol are used, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by Henkel, or else polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by Uniqema, and mixtures thereof.

As other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by Dow Corning under the references DC2-5185 and DC2-5225 C.

The pigments used in the dye composition according to the invention may be surface treated with an organic agent.

Thus, the pigments that have been surface treated beforehand, which are useful in the context of the invention, are pigments that have totally or partially undergone a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature, with an organic agent such as those described especially in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example caranuba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.

The surface-treated pigments that are useful in the dye composition according to the invention may also have been treated with a mixture of these compounds and/or may have undergone several surface treatments.

The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.

Preferably, the surface-treated pigments are coated with an organic layer.

The organic agent with which the pigments are treated may be deposited on the pigments by solvent evaporation, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.

The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in U.S. Pat. No. 4,578,266.

An organic agent covalently bonded to the pigments will preferably be used.

The agent for the surface treatment may represent from 0.1% to 50% by weight, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 10% by weight of the total weight of the surface-treated pigment.

Preferably, the surface treatments of the pigments are chosen from the following treatments:

-   -   a PEG-silicone treatment, for instance the AQ surface treatment         sold by LCW;     -   a methicone treatment, for instance the SI surface treatment         sold by LCW;     -   a dimethicone treatment, for instance the Covasil 3.05 surface         treatment sold by LCW;     -   a dimethicone/trimethyl siloxysilicate treatment, for instance         the Covasil 4.05 surface treatment sold by LCW;     -   a magnesium myristate treatment, for instance the MM surface         treatment sold by LCW;     -   an aluminum dimyristate treatment, such as the MI surface         treatment sold by Miyoshi;     -   a perfluoropolymethylisopropyl ether treatment, for instance the         FHC surface treatment sold by LCW;     -   an isostearyl sebacate treatment, for instance the HS surface         treatment sold by Miyoshi;     -   a perfluoroalkyl phosphate treatment, for instance the PF         surface treatment sold by Daito;     -   an acrylate/dimethicone copolymer and perfluoroalkyl phosphate         treatment, for instance the FSA surface treatment sold by Daito;     -   a polymethylhydrosiloxane/perfluoroalkyl phosphate treatment,         for instance the FS01 surface treatment sold by Daito;     -   an acrylate/dimethicone copolymer treatment, for instance the         ASC surface treatment sold by Daito;     -   an isopropyl titanium triisostearate treatment, for instance the         ITT surface treatment sold by Daito;     -   an acrylate copolymer treatment, for instance the APD surface         treatment sold by Daito;     -   a perfluoroalkyl phosphate/isopropyl titanium triisostearate         treatment, for instance the PF+ITT surface treatment sold by         Daito.

According to one particular embodiment of the invention, the dispersant is present with organic or mineral pigments in submicron-sized particulate form in the dye composition.

The term “submicron” is understood to mean pigments having a particulate size that has been micronized by a micronization method and having a mean particle size of less than a micrometer (μm), in particular between 0.1 and 0.9 μm, and preferably between 0.2 and 0.6 μm.

According to one embodiment, the dispersant and the pigment or pigments are present in an amount (dispersant:pigment) of between 0.5:1 and 2:1, particularly between 0.75:1 and 1.5:1 or better still between 0.8:1 and 1.2:1.

According to one particular embodiment, the dispersant is suitable for dispersing the pigments and is compatible with a condensation-curable formulation.

The term “compatible” is understood to mean, for example, that said dispersant is miscible in the oily phase of the composition or of the dispersion containing the pigment(s), and it does not retard or reduce the curing. The dispersant is preferably cationic.

The dispersant(s) may therefore have a silicone backbone, such as silicone polyether and dispersants of aminosilicone type. Among the suitable dispersants, mention may be made of:

-   -   aminosilicones, i.e. silicones comprising one or more amino         groups such as those sold under the names and references: BYK         LPX 21879 by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and         GP-988-1, sold by Genesee Polymers,     -   silicone acrylates such as Tego® RC 902, Tego® RC 922, Tego® RC         1041, and Tego® RC 1043, sold by Evonik,     -   polydimethylsiloxane (PDMS) silicones with carboxyl groups such         as X-22162 and X-22370 by Shin-Etsu, epoxy silicones such as         GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695         by Genesee Polymers, or Tego® RC 1401, Tego® RC 1403, Tego® RC         1412 by Evonik.

According to one particular embodiment, the dispersant(s) is (are) of aminosilicone type and are positively charged.

Preferably, the pigment(s) is (are) chosen from mineral, organic or mixed mineral-organic pigments.

The total amount of pigment(s) may range from 0.01% to 30% by weight, more particularly from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and preferably from 1% to 10% by weight relative to the total weight of the dye composition.

The dye composition of the invention may contain other colored or coloring species different from the pigments according to the invention, such as direct dyes or oxidation dye precursors.

The dye composition according to the invention advantageously comprises water, which may preferably be present in a content ranging from 15% to 90% by weight, more preferentially from 20% to 70% by weight, relative to the weight of the composition.

Organic Solvents

The dye composition according to the invention may comprise one or more organic solvents.

Examples of organic solvents that may be mentioned include lower C₁-C₄ alkanols, such as ethanol and isopropanol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether and diethylene glycol monoethyl ether and monomethyl ether, and also aromatic alcohols, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.

Preferably, the composition according to the invention comprises one or more organic solvents.

When they are present, the organic solvents are present in a total amount preferably inclusively between 0.1% and 80% by weight approximately relative to the total weight of the dye composition and more preferentially between 1% and 60% by weight and even more particularly inclusively between 5% and 50% by weight relative to the total weight of the dye composition.

Additives

The dye composition according to the invention may also contain at least one agent customarily used in cosmetics, for example chosen from reducing agents, thickeners, softeners, antifoams, moisturizers, UV-screening agents, peptizers, solubilizers, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, cationic polymers other than the cationic acrylic polymers described above.

The dye composition according to the invention may comprise one or more silicones, which may be solid or liquid, and volatile or non-volatile.

The silicones that may be used may be soluble or insoluble in the dye composition according to the invention; they may be in the form of oil, wax, resin or gum; silicone oils and gums are preferred.

Silicones are especially described in detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press.

The volatile silicones may be chosen from those with a boiling point of between 60° C. and 260° C. (at atmospheric pressure) and more particularly from:

i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms, such as

-   -   octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

Mention may be made of the products sold under the name Volatile Silicone 7207 by Union Carbide or Silbione 70045 V 2 by Rhodia, Volatile Silicone 7158 by Union Carbide or Silbione 70045 V 5 by Rhodia;

-   -   cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type         having the chemical structure:

Mention may be made of Volatile Silicone FZ 3109 sold by the company Union Carbide;

-   -   mixtures of cyclic silicones with silicon-derived organic         compounds, such as the mixture of octamethylcyclotetrasiloxane         and of tetratrimethylsilylpentaerythritol (50/50) and the         mixture of octamethylcyclotetrasiloxane and of         1,1′-oxy(2,2,2′,2′,3,3′-hexatrimethylsilyloxy)bisneopentane;     -   ii) linear polydialkylsiloxanes containing 2 to 9 silicon atoms,         which generally have a viscosity of less than or equal to 5×10⁻⁶         m²/s at 25° C., such as decamethyltetrasiloxane.

Other silicones belonging to this category are described in the article published in Cosmetics and Toiletries, Vol. 91, January 76, pages 27-32, Todd & Byers “Volatile Silicone Fluids for Cosmetics”; mention may be made of the product sold under the name SH 200 by the company Toray Silicone.

Among the non-volatile silicones, mention may be made, alone or as a mixture, of polydialkylsiloxanes and especially polydimethylsiloxanes (PDMSs), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and also organopolysiloxanes (or organomodified polysiloxanes, or alternatively organomodified silicones) which are polysiloxanes including in their structure one or more organofunctional groups, generally attached via a hydrocarbon-based group, and preferably chosen from aryl groups, amine groups, alkoxy groups and polyoxyethylene or polyoxypropylene groups.

The organomodified silicones may be polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes, functionalized with the organofunctional groups mentioned previously. The polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes.

Among the organomodified silicones, mention may be made of organopolysiloxanes including:

-   -   polyoxyethylene and/or polyoxypropylene groups optionally         including C₆-C₂₄ alkyl groups, such as dimethicone copolyols,         and especially those sold by the company Dow Corning under the         name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 711         from the company Union Carbide; or alternatively         (C₁₂)alkylmethicone copolyols, and especially those sold by the         company Dow Corning under the name Q2-5200;     -   substituted or unsubstituted amine groups, in particular C₁-C₄         aminoalkyl groups; mention may be made of the products sold         under the names GP4 Silicone Fluid and GP7100 by the company         Genesee, or under the names Q2-8220 and DC929 or DC939 by the         company Dow Corning;     -   thiol groups, such as the products sold under the names GP 72 A         and GP 71 from Genesee;     -   alkoxylated groups, such as the product sold under the name         Silicone Copolymer F-755 by SWS Silicones and Abil Wax® 2428,         2434 and 2440 by the company Goldschmidt;     -   hydroxylated groups, for instance polyorganosiloxanes containing         a hydroxyalkyl function;     -   acyloxyalkyl groups, such as the polyorganosiloxanes described         in U.S. Pat. No. 4,957,732;     -   anionic groups of the carboxylic acid type, as described, for         example, in EP 186 507, or of the alkylcarboxylic type, such as         the product X-22-3701E from Shin-Etsu; or alternatively of the         2-hydroxyalkylsulfonate or 2-hydroxyalkylthiosulfate type, such         as the products sold by Goldschmidt under the names Abil® S201         and Abil® S255;     -   hydroxyacylamino groups, such as the polyorganosiloxanes         described in patent application EP 342 834; mention may be made,         for example, of the product Q2-8413 from the company Dow         Corning.

The silicones may also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes bearing trimethylsilyl end groups.

Among these polydialkylsiloxanes, mention may be made of the following commercial products:

-   -   the Silbione® oils of the 47 and 70 047 series or the Mirasil®         oils sold by Rhodia, for instance the oil 70 047 V 500 000;     -   the oils of the Mirasil® series sold by the company Rhodia;     -   the oils of the 200 series from Dow Corning, such as DC200, with         a viscosity of 60 000 mm²/s;     -   the Viscasil® oils from General Electric and certain oils of the         SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes bearing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.

In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax® 9800 and 9801 by the company Goldschmidt, which are poly(C1-C20)dialkylsiloxanes.

Products that may be used more particularly in accordance with the invention are mixtures such as:

-   -   mixtures formed from a polydimethylsiloxane hydroxylated at the         chain end, or dimethiconol (CTFA), and from a cyclic         polydimethylsiloxane, also known as cyclomethicone (CTFA), such         as the product Q2-1401 sold by Dow Corning.

The polyalkylarylsiloxanes are chosen particularly from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1×10⁻⁵ to 5×10⁻² m²/s at 25° C.

Among these polyalkylarylsiloxanes, mention may be made of the products sold under the following names:

-   -   the Silbione® oils of the 70 641 series from Rhodia;     -   the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;     -   the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;     -   the silicones of the PK series from Bayer, such as the product         PK20;     -   the silicones of the PN and PH series from Bayer, such as the         products PN1000 and PH1000;     -   certain oils of the SF series from General Electric, such as SF         1023, SF 1154, SF 1250 and SF 1265.

The dye composition according to the invention may comprise one or more silicones in a total amount ranging from 0.01% to 30% by weight, preferably from 0.1% to 10% by weight and better still from 0.2% to 5% by weight, relative to the total weight of the dye composition.

Presentation Form

The dye composition according to the invention may especially be in the form of a suspension, a dispersion, a gel, an emulsion, especially an oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple (W/O/W or polyol/O/W or O/W/O) emulsion, in the form of a cream, a mousse, a stick, a dispersion of vesicles, especially of ionic or nonionic lipids, or a two-phase or multi-phase lotion. Preferably, the composition is in the form of a gel.

A person skilled in the art may select the appropriate presentation form, and also the method for preparing it, on the basis of his general knowledge, taking into account firstly the nature of the constituents used, especially their solubility in the support, and secondly the intended application of the composition.

The method according to the invention comprises a step of applying a makeup-removing composition to dyed keratin fibers such as the hair. This step may take place following the dyeing of the keratin fibers by the dye composition according to the invention, or after a defined time, i.e. days or weeks, after the application of the dye composition to the keratin fibers.

Makeup-Removing Composition

The makeup-removing composition may be in the form of an emulsion, a microemulsion, a two-phase composition or an anhydrous composition.

The term “anhydrous composition” means a composition which contains less than 2% by weight of water, or even less than 0.5% of water relative to the total weight of the composition, or in particular a composition free of water, the water not being added during the preparation of the composition but corresponding to the residual water provided by the mixed ingredients.

When the composition according to the invention is an emulsion, a microemulsion or a two-phase composition, it comprises an aqueous phase and an oily phase. The emulsions or microemulsions, on the one hand, and the two-phase compositions on the other hand, according to the invention are distinguished by the fact that the two-phase compositions are constituted of two phases which, at rest, are visibly distinct from one another other instead of being emulsified in one another.

When the composition is in the form of an emulsion, it may be a water-in-oil (W/O) or oil-in-water (O/W) emulsion, or a multiple (W/O/W or O/W/O) emulsion.

“Microemulsion” denotes a thermodynamically stable isotropic single liquid phase containing a ternary system having three components comprising an oily component, an aqueous component and a surfactant. In the present context, the term “microemulsion” denotes a “microemulsion in the narrow sense”, i.e. a thermodynamically stable isotropic single liquid phase.

The microemulsion may be of O/W (oil-in-water) type in which the oil is solubilized by micelles, a microemulsion of W/O (water-in-oil) type in which the water is solubilized by reverse micelles, or a bicontinuous microemulsion in which the number of associations of surfactant molecules tends to infinity such that the aqueous phase and the oily phase both have a continuous structure.

The microemulsion may have a dispersed phase with a number-average diameter of 100 nm or less, preferably 50 nm or less and more preferably 20 nm or less, measured by laser particle size analysis.

Preferably, the makeup-removing composition according to the invention is in the form of a water-in-oil emulsion or a water-in-oil microemulsion.

More preferentially, the makeup-removing composition according to the invention is in the form of a water-in-oil microemulsion.

Oily Phase

Preferably, the makeup-removing composition comprises an oily phase.

The content of oily phase in the makeup-removing composition varies according to the formulation of the makeup composition (emulsion, microemulsion, anhydrous, etc.).

The oily phase comprises at least one hydrocarbon oil and may further comprise one or more fatty substances other than the hydrocarbon oils as described below.

Hydrocarbon Oil

The makeup-removing composition according to the invention comprises at least one hydrocarbon oil. Preferably, the oily phase of the makeup-removing composition comprises at least one hydrocarbon oil.

The term “oil” means a fatty substance that is liquid at room temperature (25° C.) and at atmospheric pressure (760 mmHg or 1.013×10⁵ Pa).

The term “fatty substance” means an organic compound that is insoluble in water at ordinary temperature (25° C.) and at atmospheric pressure (760 mmHg or 1.013×10⁵ Pa) (solubility of less than 5%, preferably of less than 1% and even more preferentially of less than 0.1%). They bear in their structure at least one hydrocarbon-based chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.

The term “hydrocarbon oil” means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

Mention may be made of volatile hydrocarbon oils and non-volatile hydrocarbon oils.

The term “non-volatile oil” means an oil that remains on the skin or the keratin fiber at room temperature and atmospheric pressure. More precisely, a non-volatile oil has an evaporation rate strictly less than 0.01 mg/cm²/min.

To measure this evaporation rate, 15 g of oil or of oil mixture to be tested are placed in a crystallizing dish 7 cm in diameter, which is placed on a balance in a large chamber of about 0.3 m³ that is temperature regulated, at a temperature of 25° C., and hygrometry regulated, at a relative humidity of 50%. The liquid is allowed to evaporate freely, without stirring it, while providing ventilation by means of a fan (Papst-Motoren, reference 8550 N, rotating at 2700 rpm) placed in a vertical position above the crystallizing dish containing said oil or said mixture, the blades being directed toward the crystallizing dish, 20 cm away from the bottom of the crystallizing dish. The mass of oil remaining in the crystallizing dish is measured at regular intervals. The evaporation rates are expressed in mg of oil evaporated per unit of area (cm²) and per unit of time (minutes).

The non-volatile hydrocarbon oils that are suitable for the present invention may be chosen in particular from:

-   -   hydrocarbon oils of plant origin, such as triglycerides         constituted of fatty acid esters of glycerol, the fatty acids of         which may have chain lengths ranging from C₄ to C₂₈, these fatty         acids possibly being linear or branched, and saturated or         unsaturated; these oils are in particular wheatgerm oil,         sunflower oil, beauty-leaf oil, grapeseed oil, sesame oil, corn         oil, apricot oil, castor oil, shea oil, avocado oil, olive oil,         soybean oil, sweet almond oil, cottonseed oil, hazelnut oil,         macadamia oil, jojoba oil, palm oil, alfalfa oil, poppy oil,         pumpkin oil, marrow oil, rapeseed oil, blackcurrant oil, evening         primrose oil, millet oil, barley oil, quinoa oil, rye oil,         safflower oil, candlenut oil, passion flower oil and musk rose         oil; or alternatively caprylic/capric acid triglycerides such as         those sold by the company Stéarineries Dubois or those sold         under the names Miglyol 810®, 812® and 818® by the company         Sasol;     -   synthetic ethers having from 10 to 40 carbon atoms;     -   linear or branched hydrocarbons, of mineral or synthetic origin,         such as petroleum jelly, polybutenes, polydecenes and squalane;     -   synthetic esters and/or ethers such as the oils of formula         R₁COOR₂ and/or R₁OR₂ in which R₁ represents the residue of a         linear or branched fatty acid comprising from 1 to 40 carbon         atoms and R₂ represents a hydrocarbon chain, in particular a         branched hydrocarbon chain containing from 1 to 40 carbon atoms,         on condition that the total number of carbons of R₁+R₂ is ≥10,         such as for example purcellin oil (cetostearyl octanoate),         isopropyl myristate, isopropyl palmitate, butyl stearate, C₁₂ to         C₁₅ alkyl benzoate, hexyl laurate, diisopropyl adipate, isononyl         isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate,         2-octyldecyl palmitate, 2-octyldodecyl myristate or lactate,         2-diethylhexyl succinate, isostearyl isostearate, octanoates,         decanoates or ricinoleates of alcohols or of polyalcohols, such         as propylene glycol dioctanoate; hydroxylated esters such as         isostearyl lactate and diisostearyl malate; lanolic acid, oleic         acid, lauric acid or stearic acid esters; glyceryl or diglyceryl         triisostearate; and pentaerythritol esters;     -   fatty alcohols that are liquid at room temperature, containing a         branched and/or unsaturated carbon chain having from 12 to 26         carbon atoms, for instance cetanol, octyldodecanol, stearyl         alcohol, linoleyl alcohol, linolenyl alcohol, isostearyl         alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol or         2-undecylpentadecanol;     -   fatty acids such as myristic acid, palmitic acid, stearic acid,         behenic acid, oleic acid, linoleic acid, linolenic acid and         isostearic acid; and     -   mixtures thereof.

Preferably, the makeup-removing composition according to the invention comprises a total content of non-volatile hydrocarbon oil(s) ranging from 10% to 95% by weight, preferably from 20% to 80% by weight, and preferentially from 30% to 70% by weight, relative to the total weight of the makeup-removing composition.

The term “volatile oil” means an oil that can evaporate on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a cosmetic volatile oil, which is liquid at room temperature. More specifically, a volatile oil has an evaporation rate of between 0.01 and 200 mg/cm²/min, limits included.

The volatile hydrocarbon oils suitable for the invention may be chosen from hydrocarbon oils having from 7 to 16 carbon atoms. The volatile hydrocarbon oils may be chosen from branched alkanes and linear alkanes.

Volatile hydrocarbon oils having from 7 to 16 carbon atoms that may especially be mentioned include branched C₈-C₁₆ alkanes, for instance C₈-C₁₆ isoalkanes (also known as isoparaffins), isododecane, isodecane, isohexadecane and, for example, the oils sold under the trade name Isopar or Permethyl, branched C₈-C₁₆ esters, for instance isohexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon oil having from 7 to 16 carbon atoms is chosen from isododecane, isodecane and isohexadecane, and mixtures thereof, and is especially isododecane.

As volatile hydrocarbon oils that may be used for the purposes of the present invention, mention may be made of linear alkanes, preferably of plant origin, comprising from 7 to 15 carbon atoms, in particular from 9 to 14 carbon atoms and more particularly from 11 to 13 carbon atoms.

As examples of linear alkanes that are suitable for the invention, mention may be made of n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14) and n-pentadecane (C15), and mixtures thereof, and in particular the mixture of n-undecane (C11) and n-tridecane (C13) described in Example 1 of patent application WO 2008/155 059 by the company Cognis. Mention may also be made of n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references, respectively, Parafol 12-97 and Parafol 14-97, and also mixtures thereof.

In this case, the makeup-removing composition according to the invention comprises a total content of volatile hydrocarbon oil(s) ranging from 0.1% to 10% by weight and better still from 0.5% to 5% by weight, relative to the total weight of the makeup-removing composition.

The hydrocarbon oil(s) according to the invention may also be defined according to their molecular weight and their solubility parameter δa.

Preferably, a hydrocarbon oil according to the invention has a molecular weight of less than or equal to 400 g/mol and a solubility parameter δa ranging from 2 to 15 J^(0.5)/cm^(1.5).

The definition and calculation of the solubility parameters in the Hansen three-dimensional solubility space are described in the article by C. M. Hansen: “The three-dimensional solubility parameters”, J. Paint Technol. 39, 105 (1967).

According to this Hansen space:

-   -   δd characterizes the London dispersion forces derived from the         formation of dipoles induced during molecular impacts;     -   δp characterizes the Debye interaction forces between permanent         dipoles and also the Keesom interaction forces between induced         dipoles and permanent dipoles;     -   δh characterizes the specific interaction forces (such as         hydrogen bonds, acid/base, donor/acceptor, etc.);         -   δa is determined by the equation δa=(δp²+δh²)^(1/2)

The parameters δd, δp, δh and δa are expressed in (J/cm³)^(1/2).

The total solubility parameter δ according to the Hansen solubility space is defined in the article “Solubility parameter values” by Eric A. Grulke in the book “Polymer Handbook”, 3rd Edition, Chapter VII, pages 519-559, by the relationship: δ=(δd ² +δp ² +δh ²)^(1/2)

Among the hydrocarbon oils having a molecular weight of less than or equal to 400 g/mol and a solubility parameter δa ranging from 2 to 15 J^(0.5)/cm^(1.5), mention may be made of dicaprylyl ether (δa=3.45 J^(0.5)/cm^(1.5)), 2-ethylhexyl palmitate (δa=4.2 J^(0.5)/cm^(1.5)), cetyl 2-ethylhexanoate (δa=4.2 J^(0.5)/cm^(1.5)), octyldodecyl neopentanoate (δa=4.2 J^(0.5)/cm^(1.5)), isostearyl neopentanoate (δa=4.3 J^(0.5)/cm^(1.5)), isostearyl benzoate (δa=4.4 J^(0.5)/cm^(1.5)), tridecyl isononanoate (δa=4.4 J^(0.5)/cm^(1.5)), isopropyl stearate (δa=4.5 J^(0.5)/cm^(1.5)), isopropyl isostearate (δa=4.5 J^(0.5)/cm^(1.5)), isopropyl palmitate (δa=4.7 J^(0.5)/cm^(1.5)), isononyl isononanoate (δa=4.87 J^(0.5)/cm^(1.5)), C12-15 alkyl benzoate (δa=4.9 J^(0.5)/cm^(1.5)), isopropyl myristate (δa=5.0 J^(0.5)/cm^(1.5)), 2-ethylhexyl 2-ethylhexanoate (δa=5.2 J^(0.5)/cm^(1.5)), isodecyl neopentanoate (δa=5.3 J^(0.5)/cm^(1.5)), 2-ethylhexyl benzoate (δa=5.9 J^(0.5)/cm^(1.5)), caprylyl carbonate (δa=6.0 J^(0.5)/cm^(1.5)) sold under the name Cetiol CC by Cognis, dioctyl (2-ethylhexyl) carbonate (δa=6.0 J^(0.5)/cm^(1.5)), diethylhexyl adipate (δa=6.2 J^(0.5)/cm^(1.5)), octadecyl 5-oxo-L-prolinate (δa=6.2 J^(0.5)/cm^(1.5)), propylene glycol dipelargonate (δa=6.4 J^(0.5)/cm^(1.5)), neopentyl glycol dicaprate (δa=6.4 J^(0.5)/cm^(1.5)), dicaprylyl maleate (δa=6.6 J^(0.5)/cm^(1.5)), propylene glycol dioctanoate (δa=6.7 J^(0.5)/cm^(1.5)), dodecyl 1-butyl-5-oxopyrrolidine-3-carboxylate (δa=7.1 J^(0.5)/cm^(1.5)), 2,4-methyl-1,5-pentanediol dineopentanoate (δa=7.3 J^(0.5)/cm^(1.5)), 2-octyldodecanol (δa=7.7 J^(0.5)/cm^(1.5)), isostearyl alcohol (δa=8.1 J^(0.5)/cm^(1.5)), oleyl alcohol (δa=8.2 J^(0.5)/cm^(1.5)), diisopropyl adipate (δa=8.31 J^(0.5)/cm^(1.5)), diisobutyl adipate (δa=8.31 J^(0.5)/cm^(1.5)), hexyldecanol (δa=8.6 J^(0.5)/cm^(1.5)), propan-2-yl 1-(2-ethylhexyl)-5-oxopyrrolidine-3-carboxylate (δa=8.6 J^(0.5)/cm^(1.5)), propylene glycol monoisostearate (δa=8.7 J^(0.5)/cm^(1.5)), isostearyl lactate (δa=8.7 J^(0.5)/cm^(1.5)), butyl 1-butyl-5-oxopyrrolidine-3-carboxylate (δa=9.4 J^(0.5)/cm^(1.5)), 2-butyloctanol (δa=9.8 J^(0.5)/cm^(1.5)), C12-C13 alkyl lactate (δa=10.1 J^(0.5)/cm^(1.5)), dimethyl isosorbide (δa=10.76 J^(0.5)/cm^(1.5)), tributyl citrate (δa=11.41 J^(0.5)/cm^(1.5)), triethyl citrate (δa=13.7 J^(0.5)/cm^(1.5)), phenylethyl alcohol (δa=14.0 J^(0.5)/cm^(1.5)), PEG-8 (polyethylene glycol containing 8 ethylene glycol units) (δa=14.8 J^(0.5)/cm^(1.5)), and mixtures thereof.

According to one preferred embodiment, the makeup-removing composition comprises at least one hydrocarbon oil having a molecular weight of less than or equal to 400 g/mol and a solubility parameter δ_(a) ranging from 2 to 15 J^(0.5)/cm^(1.5), said oil being chosen preferably from synthetic ethers and esters, and preferably from isopropyl myristate (δ_(a)=5.0 J^(0.5)/cm^(1.5)), dicaprylyl ether (δ_(a)=3.45 J^(0.5)/cm^(1.5)), isononyl isononanoate (δ_(a)=4.87 J^(0.5)/cm^(1.5)), isodecyl neopentanoate (δ_(a)=5.3 J^(0.5)/cm^(1.5)), diisobutyl adipate (δ_(a)=8.31 J^(0.5)/cm^(1.5)), diisopropyl adipate (δ_(a)=8.31 J^(0.5)/cm^(1.5)), dimethyl isosorbide (δ_(a)=10.76 J^(0.5)/cm^(1.5)), tributyl citrate (δ_(a)=11.41 J^(0.5)/cm^(1.5)), and mixtures thereof.

Preferably, the makeup-removing composition comprises at least one non-volatile hydrocarbon oil.

Preferably, the makeup-removing composition comprises at least one hydrocarbon oil chosen from synthetic esters of formula R₁COOR₂ in which R₁ represents the residue of a fatty acid comprising from 8 to 29 carbon atoms and R₂ represents a branched or unbranched hydrocarbon chain, containing from 3 to 30 carbon atoms, and mixtures thereof.

More preferentially, the hydrocarbon oil(s) are chosen from isopropyl myristate, isononyl isononanoate, and mixtures thereof.

Preferably, the hydrocarbon oil(s) is (are) present in a total content ranging from 10% to 95% by weight, better still from 20% to 80% by weight, and more preferentially from 30% to 70% by weight, relative to the total weight of the makeup-removing composition.

The oily phase is present in a content of between 0.1% and 80% by weight, preferably between 1% and 70% by weight, relative to the total weight of the makeup-removing composition.

Aqueous Phase

Preferably, the makeup-removing composition comprises an aqueous phase.

The aqueous phase comprises water. It may also comprise at least one water-soluble organic solvent.

The term “water-soluble organic solvent” means an organic solvent that is miscible with water at 25° C.

Among the water-soluble organic solvents that may be used in the makeup-removing composition, mention may be made especially of monoalcohols having from 1 to 5 carbon atoms such as ethanol, isopropanol and butanol, and glycols having from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol.

Preferably, the aqueous phase (water and optionally the water-miscible solvent) is then present in the makeup-removing composition in a content ranging from 0.5% to 30% by weight, relative to the total weight of the makeup-removing composition, more preferentially ranging from 1% to 20% by weight, and better still from 5% to 15% by weight, relative to the total weight of the makeup-removing composition.

When the makeup-removing composition according to the invention comprises water, the water content preferably varies from 0.5% to 30% by weight, preferentially from 1% to 20% by weight and better still from 2% to 10% by weight, relative to the total weight of the makeup-removing composition.

Surfactants

The makeup-removing composition may comprise one or more surfactants.

The surfactant may be chosen from nonionic surfactants, anionic surfactants, amphoteric or zwitterionic surfactants, and mixtures thereof.

Mention may be made, as surfactants that can be used in the makeup-removing composition according to the invention:

-   -   among the nonionic surfactants, of:     -   glycerol ethers which are preferably oxyalkylenated,         oxyethylenated and/or oxypropylenated, which may comprise from         10 to 150 oxyethylene and/or oxypropylene units;     -   oxyalkylenated alcohols, in particular oxyethylenated and/or         oxypropylenated alcohols, which may comprise from 2 to 150         oxyethylene and/or oxypropylene units, preferably from 5 to 100         oxyethylene units, in particular ethoxylated C₈-C₂₄ and         preferably C₁₂-C₁₈ fatty alcohols such as ethoxylated stearyl         alcohol comprising 20 oxyethylene units (CTFA name: Steareth-20)         such as Brij 78 sold by the company Uniqema, or ethoxylated         cetearyl alcohol comprising 30 oxyethylene units (CTFA name:         Ceteareth-30) and the mixture of C₁₂-C₁₅ fatty alcohols         comprising 7 oxyethylene units (CTFA name: C12-15 Pareth-7), for         instance the product sold under the name Neodol 25-7® by Shell         Chemicals;     -   esters of a fatty acid, especially a C₈-C₂₄ and preferably         C₁₆-C₂₂ fatty acid, and of polyethylene glycol (or PEG) (which         may comprise from 10 to 150 oxyethylene units), such as PEG-50         stearate and PEG-40 monostearate sold under the name Myrj 52P®         by the company Uniqema;     -   esters of a fatty acid, especially a C₈-C₂₄ and preferably         C₁₆-C₂₂ fatty acid, and of glycerol ethers which are preferably         oxyalkylenated, oxyethylenated and/or oxypropylenated (which may         comprise from 10 to 150 oxyethylene and/or oxypropylene units),         for instance polyoxyethylenated glyceryl monostearate comprising         200 oxyethylene units, sold under the name Simulsol 220 TM® by         the company SEPPIC; polyoxyethylenated glyceryl stearate         comprising 30 oxyethylene units, for instance the product Tagat         S® sold by the company Goldschmidt, polyoxyethylenated glyceryl         oleate comprising 30 oxyethylene units, for instance the product         Tagat O® sold by the company Goldschmidt, polyoxyethylenated         glyceryl cocoate comprising 30 oxyethylene units, for instance         the product Varionic LI 13® sold by the company Sherex,         polyoxyethylenated glyceryl isostearate comprising 30         oxyethylene units, for instance the product Tagat L® sold by the         company Goldschmidt, and polyoxyethylenated glyceryl laurate         comprising 30 oxyethylene units, for instance the product Tagat         I® from the company Goldschmidt;     -   esters of a fatty acid, especially a C₈-C₂₄ and preferably         C₁₆-C₂₂ fatty acid, and of sorbitol ethers which are preferably         oxyalkylenated, oxyethylenated and/or oxypropylenated (which may         comprise from 2 to 150 oxyethylene and/or oxypropylene units),         for instance the polysorbate 60 sold under the name Tween 60® by         the company Uniqema or the polysorbate 21 old under the name         Tween 21-LQ® by the company Croda;     -   and mixture(s) thereof.     -   among the anionic surfactants, of:     -   alkyl phosphates;     -   alkyl sulfates, and in particular alkyl ether sulfates,         alkylamido ether sulfates, alkylaryl polyether sulfates and         monoglyceride sulfates;     -   alkyl sulfonates, alkylamide sulfonates, alkylaryl sulfonates,         α-olefin sulfonates, paraffin sulfonates;     -   alkyl sulfosuccinates, alkyl ether sulfosuccinates and         alkylamide sulfosuccinates;     -   alkyl sulfosuccinamates;     -   alkyl sulfoacetates;     -   acyl sarcosinates, acyl glutamates, acyl isethionates, N-acyl         taurates and acyl lactylates;     -   alkylpolyglycoside carboxylic esters, such as alkylglucoside         citrates, alkylpolyglycoside tartrates, alkylpolyglycoside         sulfosuccinates or alkylpolyglycoside sulfosuccinamates; and     -   fatty acids, and salts thereof, in particular oleic acid,         ricinoleic acid, palmitic acid or stearic acid salts, coconut         oil or hydrogenated coconut oil acids;     -   alkyl-D-galactoside uronic acids and salts thereof,         polyoxyalkylenated (C6-C24)alkyl ether carboxylic acids,         polyoxyalkylenated (C₆-C₂₄)alkylaryl ether carboxylic acids,         polyoxyalkylenated (C₆-C₂₄)alkylamido ether carboxylic acids and         salts thereof, in particular those containing from 2 to 50         alkylene oxide and in particular ethylene oxide groups;     -   and mixtures thereof; preferably from fatty acid salts.     -   among amphoteric or zwitterionic surfactants, of:

alkylamphoacetates such as N-disodium N-cocoyl-N-carboxymethoxyethyl-N-carboxymethylethylenediamine (CTFA name: Disodium cocoamphodiacetate) sold as an aqueous saline solution under the name Miranol C2M Conc NP by the company Rhodia Chimie; N-sodium N-cocoyl-N-hydroxyethyl-N-carboxymethylethylenediamine (CTFA name: sodium cocamphoacetate); cocamides, for instance the mixture of coconut acid ethanolamides (CTFA name: Cocamide DEA).

Preferably, the surfactant(s) are chosen from nonionic surfactants.

Preferably, the nonionic surfactant(s) are chosen from esters of a C₈-C₂₄ and preferably C₁₆-C₂₂ fatty acid, and of sorbitol ethers which are preferably oxyalkylenated, oxyethylenated and/or oxypropylenated.

Preferably, the makeup-removing composition comprises at least one nonionic surfactant chosen from esters of a fatty acid, especially a C₈-C₂₄ and preferably C₁₆-C₂₂ fatty acid, and of preferably oxyalkylenated, oxyethylenated and/or oxypropylenated sorbitol ethers.

Preferably, when the makeup-removing composition comprises one or more surfactants, the total amount of surfactant(s) ranges from 1% to 50% by weight, more preferentially from 5% to 45% by weight and better still from 10% to 35% by weight, relative to the total weight of the makeup-removing composition.

Additives

The makeup-removing composition may also contain any adjuvant or additive usually used.

Among the additives that may be contained in the makeup-removing composition, mention may be made in particular of preservatives, antioxidants, fragrances, mattifying fillers, cosmetic active agents, thickeners, lipophilic or hydrophilic polymers and sequestrants.

Method for Dyeing and Removing Makeup from and/or Cleansing Keratin Fibers

The present invention relates to a method for treating human keratin fibers such as the hair comprising a step of applying to the keratin fibers a dye composition as described above and a step of applying, to the dyed keratin fibers, a makeup-removing composition as defined above.

The application of the dye composition to the keratin fibers is carried out before the application of the makeup-removing composition.

The dye composition according to the invention may be used on wet or dry keratin fibers, and also on any type of fair or dark, natural or dyed, permanent-waved, bleached or straightened fibers.

According to a particular embodiment of the method of the invention, the fibers are washed before application of the dye composition described above.

The dyeing method, i.e. application of the dye composition to the keratin fibers, is generally carried out at room temperature (between 15 and 25° C.).

After the application of the dye composition, the fibers may be left to dry or dried, for example at a temperature above or equal to 30° C. According to a particular embodiment, this temperature is above 40° C. According to a particular embodiment, this temperature is above 45° C. and below 220° C.

Preferably, if the fibers are dried, they are dried, in addition to a supply of heat, with a flow of air. This flow of air during drying makes it possible to improve the strand separation of the coating.

During drying, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through. This operation may likewise be carried out once the fibers have dried, naturally or otherwise.

The drying step of the method of the invention may be carried out with a hood, a hairdryer, a straightening iron, a Climazone.

When the drying step is carried out with a hood or a hairdryer, the drying temperature is between 30° C. and 110° C., preferably between 50° C. and 90° C.

When the drying step is carried out with a straightening iron, the drying temperature is between 110° C. and 220° C., preferably between 140° C. and 200° C.

Preferably, the method according to the invention comprises a step of applying heat to the keratin fibers using a heating tool, at a temperature ranging from 40° C. to 220° C., preferentially from 50° C. to 220° C. and more preferentially from 100° C. to 210° C., wherein the application of heat to the keratin fibers is carried out after the application of the dye composition and before the application of the makeup-removing composition to the keratin fibers.

The makeup-removing composition is applied to keratin fibers dyed with the dye composition as defined above.

The application of the makeup-removing composition can be carried out on dry dyed keratin fibers or wet dyed keratin fibers and also on all types of fibers.

The makeup-removing method is generally carried out at room temperature (between 15° C. and 25° C.).

The application of the makeup-removing composition may be carried out immediately after the application of the dye composition (i.e. a few minutes to a few hours after the application of the dye composition), or in the days or weeks following the application of the dye composition.

The makeup-removing composition may be applied with the aid of any suitable support, which is especially capable of absorbing it, for example a fibrous makeup-removing disk, a woven or nonwoven fabric, cotton wool, a flocked film, a sponge, a wipe, or a twisted or injection-molded mascara application brush.

The makeup-removing composition may be contained in a container and taken up gradually each time makeup is removed. As a variant, the makeup-removing composition impregnates the support used for removing makeup, the support possibly being packaged, in this case, for example in leaktight packaging.

After the makeup-removing composition has been used, the keratin fibers may not be rinsed. As a variant, they may be rinsed. The rinsing may be performed, for example, with running water, without addition of a soap.

The present invention will now be described more specifically by means of examples, which do not in any way limit the scope of the invention. However, the examples make it possible to support specific characteristics, variants and preferred embodiments of the invention.

EXAMPLE Example 1

Dye Composition

Compositions (g/100 g)

Composition A (invention) Polyquaternium 99 (containing 30 30% active material in ethanol)⁽¹⁾ Ethanol 22.34 Carbon Black (CI 77266) (in aqueous 12 dispersion containing 25% active material) water qs 100 ⁽¹⁾sold under the trade name Plascize L-514 by GOO Chemical

Protocol:

The dye composition A is applied to locks of natural hair containing 90% white hairs in a proportion of 0.5 g of composition per gram of lock.

The locks of hair are then combed and dried with a hairdryer.

A straightening iron is then passed over each of the locks five times at a temperature of 190° C.

The hair is dyed uniformly and intensely.

The hair thus dyed is then subjected to a test of several repeated shampoo washes so as to evaluate the persistence (resistance) of the coloring obtained with respect to shampoo washes.

Shampoo Wash Protocol:

The locks are washed with standard shampoo respectively at T=0 (i.e. after the application of the dye composition to the keratin fibers and after the application of the straightening iron to the locks of hair).

The locks of hair are then rinsed, combed and dried with a hairdryer.

Lastly, a straightening iron is then passed over each of the locks five times at a temperature of 190° C.

The next shampoo wash is then performed on the locks obtained after the passes of the straightening iron.

Results:

The resistance of the color of the locks was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600D colorimeter.

In this L*a*b* system, L* represents the intensity of the color, a* indicates the green/red color axis and b* the blue/yellow color axis.

The resistance of the coloring is evaluated by the color difference ΔE between the dyed locks before shampooing, then after having undergone 3 and 10 shampoo washes according to the protocol described above. The lower the value of ΔE, the more shampoo-resistant the color.

Number of shampoo washes L* a* b* ΔE 0 26 1 2 3 33 1 4 7.3 10 38 1 6 12.7

The hair has a natural feel and the strands of hair may be separated with the fingers or by using a comb and/or a brush.

In addition, the hair is dyed and the locks of hair dyed with the dye composition A and washed with three or ten shampoo washes have low values of ΔE. Thus, the colored coating of the keratin fibers is shampoo-resistant. Specifically, the locks of hair washed with three or ten shampoo washes have a good color persistence.

Makeup-Removing Composition

Compositions (g/100 g)

Composition B (invention) Polysorbate 21 30 Isopropyl myristate 30 Isononyl isononanoate 30 Ethanol 3 Caprylyl glycol 0.5 preservative qs water qs 100

Protocol:

The locks of hair dyed by the dye composition A are treated with the makeup-removing composition B once the dyed locks are dry to the touch, in a proportion of 0.5 g of composition B per gram of lock.

The locks of hair dyed by the dye composition A are rinsed with the makeup-removing composition B three times in succession. Between each application of the makeup-removing composition, the locks are rinsed with water.

After the three applications of the makeup-removing composition, the locks are placed on absorbent paper and dried with a hairdryer.

Results:

As the number of washes with the makeup-removing composition increases, the hair is rapidly bleached.

Example 2

Dye Composition

Compositions (g/100 g) AM Active Material

C D Composition (invention) (comparative) Polyquaternium 99 (containing 30% 9 AM (30 g) — active material in ethanol)⁽¹⁾ Acrylates/octylacrylamide copolymer — 9 AM (containing 97% active material in water) ⁽²⁾ Carbon Black (CI 77266) (in aqueous 12 12 dispersion containing 25% active material) ethanol qs 100 qs 100 ⁽¹⁾sold under the trade name Plascize L-514 by GOO Chemical ⁽²⁾ sold under the trade name DERMACRYL 79 by Akzo Nobel

Protocol:

The dye compositions C and D are applied to locks of natural hair containing 90% white hairs in a proportion of 0.5 g of composition per gram of lock.

The locks of hair are then combed and dried with a hairdryer.

A straightening iron is then passed over each of the locks five times at a temperature of 190° C.

The hair is dyed uniformly and intensely.

The hair thus dyed is then subjected to a test of several repeated shampoo washes so as to evaluate the persistence (resistance) of the coloring obtained with respect to shampoo washes.

Results:

The resistance of the color of the locks was evaluated in the CIE L*a*b* system, using a Konica Minolta CM-3600A colorimeter.

In this L*a*b* system, L* represents the intensity of the color, a* indicates the green/red color axis and b* the blue/yellow color axis.

The resistance of the coloring is evaluated by the color difference ΔE between the dyed locks before shampooing, and then after having undergone 3 shampoo washes according to the protocol described in example 1. The lower the value of ΔE, the more shampoo-resistant the color.

Number of shampoo Composition washes L* a* b* ΔE Composition C 0 21.5 0.4 2 (invention) 3 22.8 0.2 2.1  1.3 Composition D 0 24.3 0 1.6 — (comparative) 3 57.2 0.7 13.7 35.1

The locks of hair dyed with the dye composition C according to the invention and washed with three shampoo washes have lower values of ΔE than the locks of hair dyed with the comparative dye composition D and washed with three shampoo washes. Thus, the colored coating of the keratin fibers dyed with the dye composition C according to the invention is shampoo-resistant. Specifically, the locks of hair dyed with the dye composition C washed with three shampoo washes have a good color persistence.

Makeup-Removing Composition

Protocol:

The locks of hair dyed by the dye compositions C and D are treated with the makeup-removing composition B as described in example 1 once the dyed locks are dry to the touch, in a proportion of 0.5 g of composition B per gram of lock.

The locks of hair dyed by the dye compositions C and D are rinsed with the makeup-removing composition B three times in succession. Between each application of the makeup-removing composition, the locks are rinsed with water.

After the three applications of the makeup-removing composition, the locks are placed on absorbent paper and dried with a hairdryer.

Results:

As the number of washes with the makeup-removing composition increases, the hair dyed with compositions C or D is rapidly bleached. 

The invention claimed is:
 1. A method for treating human keratin fibers comprising: applying to the keratin fibers a first composition comprising: at least one cationic acrylic copolymer comprising: a) at least one first unit chosen from monomers derived from acrylic or methacrylic esters or amides and comprising at least one cationic group; and b) at least one second unit chosen from alkyl acrylate and/or methacrylate monomers; and at least one pigment; and applying to the keratin fibers a second composition comprising at least one hydrocarbon oil.
 2. The method of claim 1, wherein the cationic acrylic copolymer further comprises c) at least one third unit chosen from polymerizable ethylenic monomers.
 3. The method of claim 2, wherein the at least one third unit is chosen from polymerizable ethylenic monomers of formula (A′):

wherein in formula (A′), R and R′, which may be identical or different, are chosen from a hydrogen atom or a C₁-C₁₀ alkyl radical; and x ranges from 1 to
 10. 4. The method of claim 3, wherein in formula (A′), R is a methyl radical and R′ is an ethyl radical.
 5. The method of claim 1, wherein: a) the at least one first unit is chosen from monomers derived from acrylic or methacrylic esters or amides and comprising at least one cationic group of the following formulae (I), (II), (III), or (IV):

wherein in formulae (I), (II), (III), and (IV): R₃ is chosen from a hydrogen atom or a CH₃ group; A is chosen from a linear or branched divalent alkyl group with 1 to 6 carbon atoms, or a hydroxyalkyl group with 1 to 4 carbon atoms; R₄, R₅, and R₆, which may be identical or different, are chosen from an alkyl group having from 1 to 18 carbon atoms or a benzyl group; R₁ and R₂, which may be identical or different, are chosen from a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; and X⁻ represents an anion derived from a mineral or organic acid, or a halide; and b) the at least one second unit is chosen from C₁-C₃₀ alkyl acrylate and/or methacrylate monomers.
 6. The method of claim 1, wherein the at least one second unit is chosen from C₁-C₁₀ alkyl acrylate and/or methacrylate monomers.
 7. The method of claim 2, wherein: a) the at least one first unit is chosen from monomers derived from acrylic or methacrylic esters or amides and comprising at least one cationic group of the following formulae (I) or (II):

wherein in formulae (I) and (II): R₃ represents a hydrogen atom or a CH₃ group; A represents a linear or branched divalent alkyl group with 1 to 6 carbon atoms, or a hydroxyalkyl group with 1 to 4 carbon atoms; R₄, R₅, and R₆, which may be identical or different, are chosen from an alkyl group having from 1 to 18 carbon atoms or a benzyl group; R₁ and R₂, which may be identical or different, are chosen from a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; and X⁻represents an anion derived from a mineral or organic acid, or a halide; b) the at least one second unit is chosen from C₁-C₃₀ alkyl acrylate or methacrylate monomer; and c) the at least one third unit is chosen from polymerizable ethylenic monomers of the following formula:

wherein in formula (A′): R and R′, which may be identical or different, are chosen from a hydrogen atom, or a C₁-C₁₀ alkyl radical; and x ranges from 1 to
 10. 8. The method of claim 2, wherein the cationic acrylic copolymer comprises units obtained from the following monomers: a) methacryloyloxyethyltrimethylammonium salt; b) butyl methacrylate; and c) ethoxyethyl methacrylate.
 9. The method of claim 1, wherein the total amount of cationic acrylic copolymers ranges from 1% to 50% by weight, relative to the total weight of the composition.
 10. The method of claim 1, wherein the total amount of pigments ranges from 0.01% to 30% by weight, relative to the total weight of the composition.
 11. The method of claim 1, wherein the first composition further comprises at least one organic solvent chosen from lower C₁-C₄ alkanols, polyols, polyol ethers, aromatic alcohols, or mixtures thereof.
 12. The method of 11, wherein the total amount of organic solvents ranges from 0.1% to 80% by weight, relative to the total weight of the composition.
 13. The method of claim 1, wherein the second composition comprises at least one non-volatile hydrocarbon oil.
 14. The method of claim 1, wherein the at least one hydrocarbon oil is chosen from synthetic esters of formula: R₁COOR₂ wherein R₁ represents the residue of a fatty acid comprising from 8 to 29 carbon atoms, and R₂ represents a branched or unbranched hydrocarbon chain containing from 3 to 30 carbon atoms.
 15. The method of claim 13, wherein the at least one non-volatile hydrocarbon oil is chosen from isopropyl myristate, isononyl isononanoate, or mixtures thereof.
 16. The method of claim 13, wherein the total amount of non-volatile hydrocarbon oils ranges from 10% to 95% by weight, relative to the total weight of the second composition.
 17. The method of claim 1, wherein the second composition further comprises at least one nonionic surfactant.
 18. The method of claim 17, wherein the at least one nonionic surfactant is chosen from esters of C₈-C₂₄ fatty acids.
 19. The method of claim 1, wherein the application of the first composition to the keratin fibers is carried out before the application of the second composition to the keratin fibers.
 20. The method of claim 1, further comprising applying heat to the keratin fibers using a heating tool having a temperature ranging from 40° C. to 220° C., wherein the application of heat is carried out after the application of the first composition to the keratin fibers and before the application of the second composition to the keratin fibers. 